Gravimetric Analysis

By: Dr. O. Rajabi (Pharm.D.- Ph.D.)

Associate Professor of Chemistry
Department of Medicinal Chemistry
Mashad University of Medical
Sciences
gravi metric
(weighing - measure)
Definition:
a precipitation or volatilization method
based on the determination of weight of a
substance of known composition that is
chemically related to the analyte

analyte - chemical element or
compound of interest
Reaction:
aA + rR -----> A
a
R
r ppt
where:
a is # of moles of analyte A
r is # of moles of reagent R
A
a
R
r
is a pure, insoluble precipitate
which we can dry and weigh or ignite
to convert to something we can weigh
ppt=precipitate
1914 Nobel Prize to
T.W.Richards (Harvard
University) for the atomic
weights of Ag, Cl, and N

Richards and his group
determined atomic weights
of 55 of the 92 known
elements using gravimetry
T.W.Richards:
Every substance must be assumed to
be impure, every reaction must be
assumed to be incomplete, every
method of measurement must be
assumed to contain some constant
error, until proof to the contrary can be
obtained.
7 Steps in Gravimetric Analysis
Dry and weigh sample
Dissolve sample
Add precipitating reagent in excess
Coagulate precipitate usually by heating
Filtration-separate ppt from mother liquor
Wash precipitate (peptization)
Dry and weigh to constant weight
Precipitation:
precipitating agent
sample
dissolved
components
Dissolve sample
Add ppting
reagent
Filter
Dry
Weigh
Suction Filtration
Filter flask
Buchner funnel
Filter paper
Glass frit
Filter adapter
Heavy-walled rubber
tubing
Water aspirator
Mother liquor
Identify insoluble form

Two considerations:
Minimize errors due to limited precipitate
solubility
Minimize errors due to precipitation process

a. Finite solubility of precipitate

ideally, K
sp
= 0 (i.e., completely insoluble)

o Some come close: ~10
-38
for Fe(OH)
3

~10
-50
for Ag
2
S

o For AgCl, K
sp
= 1.78 x 10
-10


For example:
what would be the % error introduced in gravimetric
analysis by the solubility of AgCl?




For a 0.1000 g AgCl precipitate in 200 ml H
2
O:






Note: Error is independent of mass of precipitate,
relative error will decrease as precipitate mass
increases (i.e., 0.038% error for 1.000 g AgCl)
+ -
sp
+ -
K =[Ag ][Cl ]
S=[Ag ] =[Cl ]
-5
sp
S= K =1.33x10 M
-5
-4
-4
1.33x10 molAgCl 143.32gAgCl
0.200L =3.824x10 gAgCl
1L 1molAgCl
3.824x10 g
So, %error: x100 = 0.38%
0.1000g
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b. Precipitation process

ideally, wed like a precipitate that forms quickly.
This implies:

Large, pure crystals
Low solubility
Easily filtered
Easily washed

How does precipitation occur?

1. As K
sp
is exceeded, solution becomes
supersaturated
2. At some point nucleation begins
3. At the same time, crystal growth begins
Two points to remember:
1. Crystal growth is independent of degree of supersaturation
2. Nucleation increases with degree of supersaturation



Minimization of supersaturation will produce the largest
particles

Two particle size classes

Colloids
very small
difficult to handle experimentally
Crystals
large (~ 10
-1
mm)
easily and rapidly filtered
high purity
What affects degree of supersaturation?

K
sp

Temperature
solubility as T

Reagent addition speed
slower addition gives
precipitation a chance
to begin at lower
supersaturation levels

Solution concentration
low reagent concentration
equals low supersaturation

But, even with the above precautions, we will often
obtain colloid instead of a crystal!
Keys to successful colloid precipitation:
1. Add precipitant slowly and in slight excess
2. Digest precipitate (Heat, stir, sit)

What about crystalline precipitate?
Similar to colloids:
1. Dilute solution
2. Slow precipitant addition
3. Elevated temperature
4. Heat unstirred
Contaminants can escape from crystal lattice

Increase crystal bridges
Particle Size / Filterability
produce particles large enough to be 'caught
ideally, produce crystals
avoid colloidal suspension
particle size = 1 - 100 nm
Precipitate Formation
crystallization
nucleation:
particles join to produce aggregates
crystal growth
aggregate grows and 'fall out' of solution

We want a few big chunks of precipitate!
supersaturation:
more solute than should be present in solution
relative supersaturation:
a measure of supersaturation, (Q-S)/S
Q = actual solute concentration
S = equilibrium solute concentration
Controlling Precipitation
Increase S
Increase temperature
Decrease Q
Dilute solution
Well mixed (stirring)
What Do We Get Out of
Gravimetry?
% of analyte, % A



%A = weight of analyte x 100
weight of sample

How Do We Get %A?
% A = weight of ppt x gravimetric factor (G.F.) x 100
weight of sample

G.F. = a FW[analyte]
b FW[precipitate]

G.F. = # gms of analyte per 1 gm ppt
Gravimetric Factor
X apples + Y sugar = Z apple pies

What is this relationship in chemistry?


The Gravimetric Factor
G.F. = a FW[analyte]
b FW[precipitate]

Analyte ppt G.F.
CaO CaCO
3

FeS BaSO
4

UO
2
(NO
3
)
2
.
6H
2
O U
3
O
8

Cr
2
O
3
Ag
2
CrO
4

Analyte ppt G.F.
CaO CaCO
3
CaO/CaCO
3

FeS BaSO
4
FeS/BaSO
4

UO
2
(NO
3
)
2

U
3
O
8
3UO
2
(NO
3
)
2
/U
3
O
8

Cr
2
O
3
Ag
2
CrO
4
Cr
2
O
3
/2Ag
2
CrO
4



Problem
Consider a 1.0000 g sample containing
75% potassium sulfate (FW 174.25)
and 25% MSO
4
. The sample is
dissolved and the sulfate is precipated
as BaSO
4
(FW 233.39). If the BaSO
4

ppt weighs 1.4900, what is the atomic
weight of M
2+
in MSO
4
?
ANS: Mg
2+

Answer
The hard part is setting up the correct
equation (good stoichiometry skills are
essential here!):



Rearranging and solving:

06 . 96
39 . 233 * 25 . 0
25 . 174
39 . 233 * 75 . 0
4900 . 1
+
+ =
x
) ( 12 . 24 ;
06 . 96
3475 . 58
4855 . 0
2
Mg
x
x
+
=
+
=
Problem
A mixture of mercurous chloride (FW 472.09)
and mercurous bromide (FW 560.99) weighs
2.00 g. The mixture is quantitatively reduced
to mercury metal (At wt 200.59) which
weighs 1.50 g. Calculate the % mercurous
chloride and mercurous bromide in the
original mixture.
ANS: 0.5182 g
Answer
Again, important to set up correct
equation:


Rearranging and solving:

( )
99 . 560
2 59 . 200 * 2
09 . 472
* 59 . 200 * 2
50 . 1
x x
+ =
( )
g x
x
5182 . 0
50 . 1 2 7151 . 0 8498 . 0
=
= +
Homogeneous Precipitation


(NH
2
)CO + 3 H
2
O + heat

HCOOH + OH
-
+ CO
2
+ 2 NH
4
+


High Electrolyte Concentration
to Aid Precipitation
Excess charge on colloid creates ionic
atmosphere around particle
Composition by
Gravimetric Analysis
Ni
2+
(aq) + H
2
DMG Ni(DMG)
2
+ 2 H
+


A 0.8234 g org sample produced 0.1397 g of
bis(dimethylglyoximate) nickel (II) (FW =
288.91 g/mol). Find the nickel content.
Explain how to create a large, filterable
precipitate.
Combustion Analysis
Find the empirical formula for a 13.72 mg organic
sample that produced 6.97 mg of water and 28.44
mg of carbon dioxide
Gravimetric Overview
Simple
Cheap
Glassware
Reagents
ovens, etc.
Balances
Specific
Timely (1/2 day)
Accurate
Precise (0.1-0.3 %)
Sensitive